SK172003A3 - Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group - Google Patents

Abstract

A process for the trimerisation of olefins is disclosed, comprising contacting a monomeric olefin or mixture of olefins under trimerisation conditions with a catalyst which comprises (a) a source of chromium, molybdenum or tungsten (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibana groups; and optionally (c) an activator.

Description

Olefin trimerization using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one atom selected from phosphorus, arsenic or antimony attached to at least one (hetero) hydrocarbyl group

Technical field

The invention relates to the trimerization of olefins, for example the preparation of 1-hexene by trimerization of ethylene.

BACKGROUND OF THE INVENTION

U.S. Patent No. 5,198,563 and related Phillips patents disclose chromium containing catalysts comprising monodentate amide ligands useful in olefin trimerization.

U.S. Patent 5,968,866 describes an oligomerization and / or trimerization process of ethylene using a chromium complex catalyst comprising a coordinating asymmetric tridentate phosphate, arsenic or stiban ligand (referred to herein as phosphine, arsenic or stiban and representing a phosphorus, arsenic or antimony atom bound to three hydrocarbyl groups) and aluminoxane, the product of this process being alpha-olefins rich in 1-hexene. This patent does not suggest that any of a phosphane, arsenic or stiban group be substituted; in fact, it is impossible to predict the effect that such compensation would have.

SUMMARY OF THE INVENTION

Further ligands have now been discovered which, when used in conjunction with a transition metal source III. then they are considerably more effective as trimerization catalysts than prior art catalysts, and also exhibit other advantageous properties. Catalysts containing these ligands in conjunction with a source of chromium, molybdenum or tungsten are also within the scope of the invention.

In a first category, the invention provides an olefin trimerization catalyst comprising

(a) a source of chromium, molybdenum or tungsten;

(b) a ligand comprising at least one of phosphorus, arsenic or antimony atoms attached to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, except that all of the polar substituents are a phosphane, arsenic or stiban group; and optionally an activator

The term "trimerization" in the description of the present invention refers to a catalytic monomer or mixture providing derived monomers, a reaction of a single olefinic olefin monomer, which products with elevated components from the three olefin reaction (s) from polymerization, or thereby differentiating oligomerizations which generally provide olefin distribution. products, which is controlled by the equation of the geometric series or follows the distribution of the Poisson pattern. "Trimerization includes the case where all monomer units in the trimerization product are identical, where the trimerization product consists of two different olefins (i.e., 2 equiv. Of one monomer react with 1 equiv. Of the other monomer) and also where three different monomer units react to form the product. A reaction involving more than one monomer is often referred to as co-discrimination.

It will be appreciated that the above catalyst may or may be formed prior to use in the trimerization reaction, or may be formed in situ by adding its individual components to the reaction mixtures.

In a further category, the invention provides a process for trimerizing olefins comprising contacting a monomeric olefin or olefin mixture under trimerization conditions with a catalyst comprising:

(a) a Group III to X transition metal source

(b) a ligand comprising at least one of phosphorus, arsenic or antimony atoms bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, except that all of the polar substituents are a phosphane, arsenic or stannane group; and optionally

c) activator.

It has also been found that the catalysts used in the above process have certain novel features. These catalysts, when supported on a support, have lower activity losses than the known unsupported catalysts than known catalysts. Thus, another aspect of the invention is a supported catalyst having at least 50% productivity per mole of catalyst, preferably at least 70% productivity per mole of catalyst, unless supported on a support, the catalyst preferably comprising

(a) source of transition metal III. to X. groups;

b) a ligand comprising at least one of a phosphorous, arsenic or antimony atom attached to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, except that all of these polar substituents are a phosphane, arsenic or stibane group; and optionally

c) activator.

In addition, it has been found that these catalysts have an unusually high productivity and maintain this productivity very well. According to a further aspect of the invention, the olefin trimerization catalyst has a productivity of at least 30,000 g of product per 1 mmol of catalyst per hour at 110 ° C or less and at an ethylene partial pressure of 2.1 MPa or less. A further aspect of the invention is an olefin trimerization catalyst wherein catalyst productivity deteriorates at a rate of less than 10% per hour.

In one embodiment of the process according to the invention, the catalyst used in the invention comprises another catalyst (d) suitable for the polymerization, oligomerization or other chemical transformation of olefins. In processes where this additional catalyst is present, the trimerization products are incorporated into a higher polymer or other chemical product.

The catalysts used in the trimerization process of the invention exhibit exceptionally high productivity and selectivity to 1-hexene in the product fraction containing 6 carbon atoms. High catalyst productivity results in increased process efficiency and / or reduced intrinsic levels of catalyst residues. The high selectivity of the catalysts results in easier product purification (resulting in or less expensive purification of the product or purer product). It is to be expected that these advantages can be applied both to the processes where the only catalyst component is the catalysts of the invention and to the integrated processes, for example the production of branched olefins, where more than one transition metal catalyst is used.

As regards the transition metal source III. to Group X (a), this may include a simple inorganic and organic salt, for example, halides, acetylacetonates, carboxylates, oxides, nitrates, sulfates, and the like, as well as coordination and organometallic complexes, for example chromium chloride / tetrahydrofuran complex, (benzene) tricarbonylchrom, chromhexacarbonyl, molybdenhexacarbonyl and the like. Preferably, component (a) is a source of chromium, molybdenum or tungsten; particularly preferably, the component is chromium.

The ligand of component (b) preferably has the general vzoriec (R ¹⁾ (R ²⁾ XYX ^{(R3) (R4),} wherein

X represents a phosphorus, arsenic or antimony atom;

Y is a linking group; and

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group or a substituted heterohydrocarbyl group, at least one of which has a polar substituent which is not a phosphane, arsenic or stibane group.

An alternative preferred structure for ligand component (b) is X ¹ R ¹ (R ² ) (R ³ ), wherein X and R ¹ , R ² and R ³ are as defined above, wherein at least one of R ¹ , R ² and R ³ has a polar substituent which is not a phosphane, arsenic or stiban group.

X is preferably phosphorus. For R ¹ , R ² , R ³ and R ⁴ examples of suitable hydrocarbyl groups are methyl, ethyl, ethylenyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl, xylyl, mesityl a group, biphenyl, naphthyl, anthracenyl, and the like. Examples of suitable heterohydrocarbyl groups are methoxy, ethoxy, phenoxy (ie -OC ₆ H ₅ ), tolyloxy (ie -OC ₆ H ₄ (CH ₃ )), xylyloxy, mesityloxy, dimethylamino, diethylamino, methylethylamino, thiylmethyl, thiomethyl, thiomethyl, thiomethyl, thiomethyl, thiomethyl group, etc.

Preferred are those R ¹ to R ⁴ having polar substituents substituted with aryl groups with at least one polar substituent. Suitable substituted aryl groups include substituted phenyl, substituted naphthyl, and substituted anthracenyl. A substituted phenyl group is preferred. Polar substituents include methoxy, ethoxy, isopropoxy, C 3 -C 20 alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, hydroxy, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxy, a nitro group, etc. Other suitable polar substituents include the phosphanes, arzanes, and stibanes described in U.S. Patent 5,968,866 (provided that at least one of R ¹ to R ⁴ has a polar substituent that is not one of these substituents). Most preferred are ortho-substituted phenyl groups; the ortho substituent is preferably an alkoxy group, more preferably a methoxy group or a methoxymethoxy group. The phenyl groups may be further substituted in the meta- and para- or other orthoposition groups such as hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl, halide and the like; but it is preferred that they are not substituted at these positions.

Preferably, any one of R ¹ to R ⁴ which does not have polar substituents is independently optionally substituted with phenyl groups; wherein the substituents may be a hydrocarbyl group, a heterohydrocarbyl group, a substituted hydrocarbyl group, a substituted heterohydrocarbyl group, a halogen, and the like. However, it is most preferred that all of R ¹ to R ⁴ have polar substituents as defined above which are not phosphane, arsenic or stibane groups. It is also most preferred that R ¹ to R ^{4 are the} same.

Y may be any bridging group, for example, a hydrocarbyl bridging group, a substituted hydrocarbyl bridging group, a heterohydrocarbyl bridging group, a substituted hydrocarbyl bridging group, or a substituted heterohydrocarbyl bridging group, or an inorganic bridging group including monatomic bonds, for example -O-. Optionally, Y may contain other effective donor sites. Examples of Y include methylene, 1,2-ethane, 1,2-phenylene, 1,3-propane, 1,2-catechol, 1,3-dimethylhydroazine, -N (R ⁵ ) -, wherein R ⁵ denotes a hydrocarbyl group or a hydrocarbyl group and the like. Preferably Y is -N ^(R5) -; preferably R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group.

hydrogen atom, substituted

Any of the groups R ¹ to R ⁴ may be independently bonded to one or more of them or to a bonding group Y and form together with X or X and Y a cyclic structure, the compounds described in the literature are:

Ligands are possible by methods known in the art. Examples prepared in the expertly preferred (2-methoxyphenyl) (phenyl) PN (Me) P (phenyl) 2, (2-methoxyphenyl) ₂ PN (Me) P (phenyl) ₂ , (2-methoxyphenyl) (phenyl) PN (Me) P (2-methoxyphenyl) (phenyl), (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ , (2-ethoxyphenyl) ₂ PN (Me) P (2-ethoxyphenyl) ₂ (2-isopropoxyphenyl) ₂ PN (Me) P (2-isopropoxyphenyl) ₂ (2-hydroxyphenyl) ₂ PN (Me) P (2-hydroxyphenyl) ₂ (2-nitrophenyl) ₂ PN (Me) P (2-nitrophenyl) ₂ (2, 3-dimethoxyphenyl) ₂ PN (Me) P (2,3-dimethoxyphenyl) ₂ (2,4-dimethoxyphenyl) ₂ PN (Me) P (2,4-dimethoxyphenyl) ₂ (2,6-dimethoxyphenyl) ₂ PN (Me P (2,6-dimethoxyphenyl) ₂ (2,4,6-trimethoxyphenyl) ₂ PN (Me) P (2,4,6-trimethoxyphenyl) ₂ (2-dimethoxyphenyl) (2-methylphenyl) PN (Me) P (2-Methylphenyl) ₂ , [2- (dimethylamino) phenyl] ₂ PN (Me) P [2- (dimethylamino) phenyl] ₂ (2-methoxymethoxyphenyl) ₂ PN (Me) P (2-methoxymethoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (ethyl) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (phenyl) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (Me) N (Me) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PCH ₂ P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PCH ₂ CH ₂ P (2-methoxyphenyl) ₂ tri (2-methoxymethoxyphenyl) phosphane, ie

tri (2-methoxyphenyl) phosphane.

Components (a) and (b) may be present in a ratio, and preferably the ratio is in the range of 10,000: 1 to 1:10,000; more preferably, the ratio ranges from

100: 1 to 1: 100, and particularly preferably in a ratio of from 10: 1 to 1: 100

1:10, especially from 3: 1 to 1: 3. Generally, the amounts of components (a) and (b) are approximately equal, i. the ratio of the components ranges from 1.5: 1 to 1: 1.5.

The activator (c) may be substantially any compound that generates an active catalyst with components (a) and (b). It is also possible to use a mixture of activators. Suitable compounds include organoaluminum compounds, organoboronic compounds, and inorganic acids and salts such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like. Suitable organoaluminum compounds include those compounds of formula AlR ₃ wherein each R is independently C 1 -C 12 alkyl, oxygen or halide, and compounds such as LiAlH ₄ and the like. Examples include trimethylaluminium (TMA), triethylaluminium (TEA), triisobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, ethylaluminium chloride, diethylaluminium chloride, diethylaluminium chloride, diethylaluminium chloride, diethylaluminium chloride, diethylaluminum sulphide, diethylaluminium chloride, diethylaluminum sulphide, diethylaluminum sulphide, diethylaluminum sulphide, diethyl aluminum chloride. Alumoxanes are known in the art as generally oligomeric compounds, which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. These compounds may be linear, cyclic, crosslinked or a combination thereof. It is generally believed that commercially available alumoxanes are mixtures of linear and cyclic compounds. The cyclic alumoxanes may be represented by the general formula [R ^with AlO] with linear alumoxanes of the general formula R ⁷ (R ⁸ AlO) _s , wherein s denotes a number from about 2 to 50 and wherein R ⁶ , R ⁷ and R ⁸ represent hydrocarbyl groups, preferably alkyl groups having 1 to 6 carbon atoms, for example methyl, ethyl or butyl. Preferably, they are alkylalumoxanes, for example methylalumoxane (MAO).

Particularly preferred trialkylaluminium compounds are mixtures of alkylalumoxanes and compounds, for example MAO with TMA or TIBA. In this context, it should be noted that the term "alkylalumoxane, as used herein, includes which may; %, but the corresponding MAO, as a rule, commercially available alkylalumoxanes, generally contain from about 10% to about 50% by weight, trialkylaluminium; for example, commercial contains about 10 wt. trimethylaluminium (TMA), while the commercial MMAO contains both TMA and TIBA. The amounts of alkylalumoxane reported herein include these trialkylaluminium admixtures, and it is understood that the amounts of the trialkylaluminium compounds cited herein also include amounts of compounds of formula AlR ₃ , in addition to all AlR ₃ compounds incorporated in the alkyl alumoxane, if present.

organoboronous trimethylboron, the compounds are triethylboron, triphenylboron,

Examples of suitable borroxines, NaBH 4, dimethylphenylammonium tetra (phenyl) borate, trityltetra (phenyl) borate, dimethylphenylammonium tetra (pentafluorophenyl) borate, tetrakis [(bis-3,5-trifluoromethyl) phenyl] borate H ⁺ (OEt ₂ ) 2 [(bis-3) 3,5-Trifluoromethylphenyl] trityltetra (pentafluorophenylborate tris (pentafluorophenyl) boron).

sodium, borate, and

The activator (c) may also be a compound that acts as a reducing or oxidizing agent, for example, sodium or zinc metal or the like, or oxygen or the like, or the compound may be part of activator (c).

In preparing the catalysts used in the invention, the plurality of activating compound to be used, simple tests, test samples, can be readily determined by performing, for example, preparing small ones, for which small amounts of monomer (s) are prepared to determine the activity of the catalyst produced. In general, it has been found that the amount used is sufficient to provide 0.1 atom to 20,000 atoms, preferably 1 atom to 2000 aluminum or boron atoms per 1 chromium atom. In some cases, certain components (a) and (b) may not require an activating compound (c).

The components (a) and (b) of the catalyst system used in the present invention may be added simultaneously or in the process, in any order, and in the presence or absence of monomer in any suitable solvent to provide an effective catalyst. For example, components (a), (b) and (c) of the monomer may be contacted simultaneously or components (a), (b) and (c) may be contacted simultaneously or sequentially in any order and subsequently listed in contact with the monomer or is. it is possible to add components (a) and (b) together to form an isolatable metal-ligand complex and then add to component (c) and contact the monomer, or it is possible to add components (a), (b) and (c) together formation of an isolatable metal-ligand complex which is subsequently contacted with the monomer. Suitable solvents for contacting the catalyst components or catalyst system include, but are not limited to, hydrocarbon solvents such as heptane, toluene, 1-hexane and the like. and polar solvents such as diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like.

The catalyst components (a), (b) and (c) used in the invention may be unsupported or deposited on a support material, for example silica, alumina MgCl ₂ or zirconium oxide, or on a polymer, for example polyethylene, polypropylene , polystyrene or poly (aminostyrene). An advantage of the invention is that very low productivity (product weight per mole catalyst per hour) is lost when the catalyst is supported. If desired, the catalysts may be formed in situ in the presence of a support material, or the support material may be impregnated or mixed with one or more catalyst components in advance or concurrently. The amount of support material used can vary over a wide range, for example from 100,000 g to 1 g / lg of metal present in the transition metal compound. In some cases, the carrier material may also act as an activator or as an activator component (c). Examples include carriers containing alumoxane residues and / or hydrocarbylboryl residues (see, for example, Hlatky, GG Chem. Rev.2000, 100, p.1347).

One embodiment of the invention involves the use of components (a), (b) and optionally (c) in conjunction with one or more types of catalyst or catalyst system (d) intended to polymerize olefins to trimerize olefins and subsequently incorporate part of the product (s) into a higher polymer. .

Component (d) may be one or more suitable polymerization catalysts or catalyst systems, examples of which include, but are not limited to, conventional Ziegler-Natta catalysts, metallocene catalysts, monocyclopentadienyl catalysts or limited geometry catalysts, thermally activated supported chromium oxide catalysts (e.g., Pph type catalysts). , late transition metal polymerization catalysts (for example, diimine, diphosphine and salicylaldimine icel / palladium catalysts, iron pyridine diamine and cobalt catalysts, etc.), and other so-called "single-site catalysts (SSC)".

Ziegler-Natta catalysts generally consist of two main components. One component is an alkyl or hydride of a Group I to III metal, most commonly Al (Et) ₃ or Al (iBu) ₃ or Al (Et) ₂ Cl, but also includes Grignard reagents, nutyllithium or dialkylzinc compounds. The second component is the transition metal salt IV. the most common titanium halides for example TiCl ₄ , TiCl ₃ , catalyst, if or VCl ₄ or VOCl ₃ are mixed, vanadium,

As a rule, the components in a hydrocarbon solvent may form a homogeneous or heterogeneous product. These catalysts can, if desired, be impregnated onto a support by means known to those skilled in the art and thus used in most processes known for coordinating the catalysis of polyolefins, for example in solution, suspension and gas phase. In addition to the two main components described above, it is also possible to add a certain amount of other compounds (typically electron donors) that further modify the polymerization behavior or catalyst activity.

The metallocene catalysts generally consist of transition metal complexes, most commonly based on Group IV metals, lined with cyclopentadienyl (Cp) type groups. A wide variety of structures of this type of catalysts are known, including those with substituted groups, attached groups and / or Cp groups containing a heteroatom, Cp groups fused to other ring systems and the like. Often other activators such as boranes or aluoxane are used, where the catalysts may be if desired, supported on a carrier.

Monocyclopentadienyl catalysts "with limited consist of catalysts or, as a rule, transition metal geometry, consisting of complexes most commonly based on Group IV metals, ligated to one group of the cyclopentadientyl (Cp) type, often attached to another donor group. A wide variety of structures of this type of catalyst are known, including those with substituted groups, attached groups and / or Cp groups containing a heteroatom, Cp groups fused to other ring systems, and the like, and a wide variety of bound and unbound other donor groups such as amides, amines and alkoxides. Other activators such as boranes or alumoxane are also frequently used, and these catalysts can be supported on a carrier, if desired.

A typical thermally activated chromium oxide catalyst (Phillips) utilizes a carrier material combination to which a chromium-containing material is first added, wherein at least a portion of the chromium is brought to a six-bound state by heating in the presence of molecular oxygen. The carrier generally comprises from about 80 wt% to about 100 wt% of the carrier. the silica and the remainder, if any, is selected from the group consisting of non-flammable metal oxides, for example alumina, boron oxide, magnesium oxide, toric oxide, zirconia, titanium dioxide, and a mixture of two or more of these non-flammable metal oxides. The carriers may also contain alumina, aluminum phosphate, boron phosphate and mixtures thereof or mixtures with silica. As a rule, the boron compound is added to the carrier as a trivalent chromium compound (III), for example in the form of acetate or acetylacetonate, to eliminate the toxicity of hexavalent chromium (VI). The crude catalyst is then fired in air at 250 ° C to 1000 ° C for several seconds to several hours. Thereby, at least a portion of the chromium is converted into a six-bound state. The reduction of the six-bound chromium (VI) to its active form is normally achieved by a gas-phase reaction, but can also be carried out at the end of the baking process by CO treatment at a temperature of about 350 ° C. Other compounds, such as fluorine, aluminum and / or titanium, may also be added to the crude Phillips catalysts to modify the catalysts.

Late transition metal catalysts and single-site catalysts cover a wide variety of transition metal catalyst structures (see, e.g., Britovsek, GJP et al. Angew, Chem. Int. Ed. Engl. 1999, 38, p.429; and Ittel. al.

Chem. Rev. 2000, 100, p. 1169th

Component (d) may also comprise one or more polymerization catalysts or catalyst systems, together with one or more other oligomerization catalysts or catalyst systems. Aqueous oligomerization catalysts include, but are not limited to, those that dimerize (e.g., nickel-phosphine dimerization catalysts) or trimerize olefins or otherwise oligomerize olefins such that the product exhibits a 1-olefin distribution based on a geometric series equation (e.g., pyridyldiimine iron oligomerization catalysts) and cobalt).

Component (d) may be independently carried or carried. If components (a) and (b) and optionally (c) are supported, then component (d) may be applied subsequently, at any time, or concurrently to the same carrier or may be supported by a separate carrier.

In some combinations, components (a) to (c) may be part of component (d) or may form the component (d) entirely. For example, if component (d) is a thermally activated chromium oxide catalyst, it may be component (a), i. j. a chromium source, and if component (d) contains an alumoxane activator, it may also be an optional activator (c).

Components (a), (b), (c) and (d) may be present in any molar ratio. In the context of the integrated process, (a) to (d) seems to be particularly important.

The ratio of (a) to (d) is preferably from 10,000: 1 to 1:10,000, and more preferably from 100: 1 to 1: 100. The exact ratio required will depend on the relative reactivity of the components as well as the desired properties of the product or catalyst system.

Suitable olefin monomers or combinations thereof for use in the trimerization process of the invention are hydrocarbon olefins, for example ethylene, 2 to 20 carbon atoms, internal olefins, vinylidene olefins, cyclic olefins and dienes, propylene, 1-butene, 1-pentene 1-hexene, 4-methylpentene-1,1-heptene, 1-octene, 1-nonene, 1-decene, 1undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1pentadecene 1-hexadecene, 1-heptadecene, 1- octadecene, 1nonadecene, 1-eicosene, styrene, 2-butene, 2-ethyl-1-hexene, cyclohexene, norbornene, butadiene and 1,5-hexadiene. Also polar-functional olefins may be used, for example methyl (meth) acrylate, vinyl acetate, α, ω-undecenol and the like. The preferred monomer is ethylene. It is also possible to use mixtures of this monomer, for example a 1-butene unit and two ethylene units can be co-reduced to form 8-carbon olefins or 1-hexene and ethylene can be co-reduced to form 10-carbon olefins, or 1-dodecene and ethylene can be co-diminished to form olefins having 16 carbon atoms. The combination of these co-discrimination reactions can be carried out concurrently, especially when one or more monomers are prepared in situ (for example, a mixture of ethylene and butene can be used to prepare a mixture consisting predominantly of hexenes, octenes and adenes). Techniques by which the product distribution of these reactions can be varied include controlling operating conditions (e.g., concentration, reaction temperatures, pressure, reaction time) as well as the correct choice of a particular type of process and are known to those skilled in the art. These monomers or combinations are also suitable in the presence of component (d).

The olefin monomers or mixtures of olefin monomers for trimerization may be substantially pure or may contain olefin admixtures. One embodiment of the process of the invention involves the trimerization of olefin-containing waste streams that are discharged from other chemical plants or from other stages of the same process.

When the reaction is carried out in solution or suspension, it is possible to use a diluent or solvent which is an olefin, a mixture of olefins or which is substantially inert under trimerization conditions. It would also be possible to use mixtures of inert diluents with or without one or more olefins. Preferred diluents or solvents are aliphatic and aromatic hydrocarbons and halogenated hydrocarbons such as isobutane, pentane, toluene, xylene, ethylbenzene, cumene, mesitylene, heptane, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, chlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene, dichlorobenzene. and mixtures such as isopar.

Trimerization conditions are understood, for example, to mean a solution, suspension, gas or solid phase at temperatures ranging from -100 ° C to +300 ° C, preferably from 0 ° C to +300 ° C, and more preferably from + 35 ° C to +200 And pressures in the range of atmospheric pressure and above, preferably from atmospheric pressure to 80 MPa and more preferably from 0.1 MPa to 10 MPa.

If desired, the process can be carried out at temperatures above 120 ° C, and optionally also at pressures below 30 MPa.

the activity and lower velocity of the catalyst system make it possible to use lower pressures than would be economically possible using known catalyst systems.

Higher initial deactivation of this oxygen, and water as catalytic

Regardless of the use of the trimerization technique, trimerization is generally carried out under conditions that substantially exclude the presence of other poisoning materials. Likewise, trimerization can be carried out in the presence of additives that control selectivity, increase efficiency and reduce the amount of polymer formed during the trimerization process. Suitable additives include, but are not limited to, a hydrogen or halide source such as GeCl ₄ . Possible halides include, but are not limited to, fluoride, chloride, bromide and / or iodide.

in the presence of hydrocarbon heptanes; than

Furthermore, there are several possible options for a trimerization reactor, including reactors for batch, semi-continuous and continuous operation. The trimerization and co-discrimination reactions of the invention can be carried out under a variety of operating conditions known to those skilled in the art: for example, as a homogeneous liquid phase reaction or in the absence of an inert diluent such as toluene or a biphasic liquid reaction; as a slurry reaction when the catalyst is in a form which exhibits only very low or no solubility at all; as a solid-phase reaction when substantially anhydrous olefins as reagents and / or products serve as the main reaction medium; as a gaseous reaction when at least a portion of the reacting or formed olefins are transported to or from the supported catalyst form in the gaseous state. Cooling one or more monomers or inert volatile liquids by evaporation may be used as one method to remove heat from the reaction mixture. The trimerization reaction can be carried out in known types of gas-phase reactors, for example, circulating-bed reactors, vertically or horizontally stirred-bed reactors, fixed-bed reactors or fluid-bed reactors, in liquid-phase reactors such as reactors in the form of Combinations of these reactors can be used in a continuous tank or in loop reactors. A wide variety of methods known to those skilled in the art can be used to separate and / or purify the product, reactant and catalyst, including: distillation, filtration, liquid-liquid separation, slurry settling, extraction, and the like. One or more of these methods may independently incorporate at least a trimerization reaction independently of the trimerization; with the example (or reaction) distillation being an example.

mixed or can be carried out separately and the reactions or it is possible to use a catalytic

Further, a process that includes a plurality of activity-destroying systems located between reactors integrated catalytically as a single catalyst, a reactor that is or downstream of the last reactor, or a reactor-separator-purifier may be preferred. All components, reactants, inert components and products can be used in a single application within the scope of the invention, although it often appears to be economically advantageous to recycle one or more of these materials; in the case of a catalyst system, obtaining an active catalyst system may require reconstruction of one or more catalyst components. It is also within the scope of the invention where the trimerization product can also serve as a reactant (for example, 1-hexene, prepared by trimerization of ethylene can be converted to decene products by subsequent co-discrimination with ethylene).

When using the catalysts of the invention in an integrated process that involves subsequent chemical transformation, i. with the presence of component (d), a variety of operating options are offered. These options include "in series" processes where the trimerization and the subsequent reaction are carried out in separate, interconnected reactors, optionally including a product and / or reactant recycling step between reactors, and "in situ" processes where both reaction steps are performed the same reactor. Chemical transformations including olefins are known to those skilled in the art; examples of chemical reactions that can be carried out using component (d) include, but are not limited to, polymerization and copolymerization, oligomerization, hydrogenation, hydoformylation, oxidation, hydration, sulfonation, epoxidation, isomerization, amination, cyclization, and alkylation. A typical time spent in the polymerization reactor is less than 4 hours, preferably less than 3 hours.

In the case of the "in series" method, various steps may also be incorporated between the trimerization step and the subsequent reaction steps, which also includes placing the process could be carried out in a single purification, analysis and control of the oligomerization product. A recycling step is possible between the reactors arranged in series. An example of such is trimerization of ethylene to a reactor when the catalyst comprises component (a), (b) and optionally (c), followed by polymerization of the product trimerization with ethylene in a separate, interconnected reactor to provide branched poylethylene. Another example would be the co-discrimination of ethylene and 1-butene and subsequent polymerization of the trimerization product to give poly (octene). Another example would be the trimerization of a polyethylene waste stream that contains ethylene and the subsequent introduction of the trimerization product, 1-hexene, back into the polyethylene process, where it is used as a comonomer for the production of branched polyethylene.

An example of a "in situ" process is the production of branched poylethylene catalysed by components (a), (b), (d) and optionally (c) added in any order so that the active catalyst species are derived from components (a), (b) and optionally (c) present at a point in time in the reactor simultaneously with component (d).

In-series (and in-situ) approaches can be an adaptation of current polymerization technology to process steps involving component (d). All existing, predominantly olefin, polymerization processes involving process steps conducted in multiple reactors can be adapted to this approach. a trimerization catalyst bed in the recycle loop of the gas phase polymerization process, which incorporation may be effected as a by-pass or recycle stream in a main fluidization recycle loop or in a system for degassing and isolation and recycling.

used in the manufacture of comonomers such as

If component (d) is present, then a solution, suspension, gas phase or solid phase, temperatures ranging from -100 ° C to +300 ° C and pressures such as atmospheric pressure and higher pressures may be used as polymerization conditions, in particular 0.14 MPa to 4.1 MPa. As a rule, reaction conditions have a large influence on the properties (e.g., density, melt index, yield) of the prepared polymer, and it is therefore likely that the requirements imposed on the polymer will dictate many reaction variables. The reaction temperature, preferably in processes where it is important to operate at a temperature below the sintering temperature of the polymer, will generally and preferably be selected to provide optimal conditions for the polymerization reaction. The high productivity and kinetic profile of this novel trimerization catalyst makes "in situ production of a comonomer, preferably hexene-1, commercially more attractive than previously known catalyst systems during the production of a polymer, preferably polyethylene. This is true both at typical reaction temperatures and pressures of high-content polyethylenes such as LLDPE, VLDPE and ULDPE (preferably 50 ° C to 100 ° C, depending on the polymer density), as well as when the polymerization processes used are carried out in suspension and gas phase (preferably pressures of the entire gas phase are from 1.5 MPa to 3.0 MPa and the pressures of ethylene in the gas phase are generally 10% to 70%). If desired, the catalyst can be used to polymerize ethylene at high pressure and / or high temperature when the polymer material is formed as a melt in supercritical ethylene. Preferably, the polymerization is carried out by a fluidized bed or by polymerization or under mixed-bed gas phase conditions. Also, the copolymerization is carried out in the presence of additives that control the molecular weight of the polymer or copolymer. In the case of the polymerization process according to the invention, hydrogen gas is generally used as a means for controlling the molecular weight of the polymer or copolymer.

for example, two to successive catalysts may be used

Suspension or gas phase polymerization is particularly suitable for the production of high or low density polyethylene and polypropylene. In this case, the polymerization can be carried out in a batch, continuous or semi-continuous manner. Furthermore, one or more rakers, five reactors connected in series. Different reaction conditions may then be used in different reactors, for example different temperatures or hydrogen concentrations. In cascade operation, the trimerization catalyst can be used in any or all of the polymerization reactors. When added to the first reactor and transferred to the reactors, the trimerization or subsequent reactors may be supplemented with fresh trimerization or polymerization catalysts or deactivated in subsequent reactors by adding reversible or irreversible poisons which partially or totally deactivate the trimerization catalyst, or by adding further polymerization catalysts to neo modifiers which also deactivate the trimerization catalyst.

or as particles in the same or concurrently or in any order. (a) to (d) carried and

In slurry and gas phase processes, the catalyst is typically supported and metered and transported to the polymerization zone as a particulate solid or as a dry powder (e.g., in an inert gas of ethylene or olefin), or as a slurry. In addition, an optional activator may be introduced into the polymerization zone, for example in the form of a solution introduced alone or together with a solid catalyst. Components (a) to (d) may be added to any part of the polymerization catalyst or on the same carrier particles, a physical mixture on different carriers, or may be added separately to different parts of the reactor, sequentially,

Alternatively, the components can be independently added to any portion of the polymerization reactor simultaneously or sequentially or separately. The ratio of the base monomer to the other (co) monomers has a large influence on the properties of the resulting polymer (e.g. density) and it is generally desirable that this ratio be carefully controlled. This ratio can be controlled primarily by varying the concentration or partial pressure of the base monomer and / or comonomer (s). As a rule, the concentration of the parent monomer will be controlled independently of the ratio to the comonomers (for other reasons such as efficacy), wherein the ratio (s) of the basic monomer to the comonomer can be controlled by changing the feed rate of the trimerization catalyst or by changing the reaction conditions polymerization reactions or which affect the distribution of the actually formed comonomers (for example using reversible poisons and / or activators). The ratio can be further controlled by introducing fresh comonomer into the polymerization reactor. It may be desirable to preferably flush out certain (co) monomer (s) that arise in the trimerization reaction, for example, by heating or cooling the vapor (or liquid) (or recycled) stream in the polymerization (or venting) system. This can be optimized, for example, by controlled shutdown of the compressor or by intermediate conditions in recycling or venting compressors or by the use of suitable condensation exchangers or distillation apparatuses.

The rate of addition of each component can be independently controlled to achieve the desired ratio of components to the desired density of the polymer formed. The efficiency of each component, as well as the properties of the polymer to be prepared, can also be controlled by varying the pressure, temperature, amount of hydrogen added, amount of halogenated hydrocarbon, amount of electron donor, amount of activator and / or retarder, and other suitable variables.

Upon discharge of the polymer product from the reactor, substantially all of the hydrocarbons contained and absorbed therein may be substantially removed from the polymer, or the polymer may be degassed, for example by depressurizing or washing with fresh or recycled stream, nitrogen or light hydrocarbons (e.g. ethylene). The recovered gaseous or liquid hydrocarbons can be recycled to the purification system or polymerization zone.

In a slurry with a paraffin polymer autoclave polymerization process carried out, the polymerization diluent is compatible (polymers) and catalysts, and for this purpose, for example, an alkane, especially hexane, heptane, isobutane or a mixture of hydrocarbons, or

The polymerization zone may be, for example, or a similar reaction vessel or continuous liquid-filled loop reactor, for example of the type well known in the production of polyethylene by the Phillips process, polymerization process of the invention. most preferably higher than 15 ° C. In slurry polymerization, the polymerization temperature is preferably kept below the temperature at which the polymer tends to soften or sinter in the presence of the polymerization diluent. If the temperature is allowed to rise above this value, fouling of the reactor may occur. By setting the temperature range defined above, it is possible to obtain a useful means of controlling the average molecular weight of the polymer produced. Another useful means for controlling the molecular weight is to carry out the polymerization in the presence of hydrogen gas, which acts as a chain transfer agent. In general, the higher the hydrogen concentration used, the lower the average molecular weight of the polymer formed.

use a higher temperature

In solid phase polymerization, a liquid monomer such as propylene is used as the polymerization medium.

Methods for carrying out gas-phase polymerization are known in the art. These methods generally include moving a catalyst bed or a cannon polymer bed (ie, a polymer having physical properties equal to or similar to those required for a polymer produced by the process) containing the catalyst (e.g., agitating, shaking or fluidizing) and introducing a monomer stream into the catalyst. bed under conditions in which at least a portion of the monomer in contact with the catalyst in the bed polymerizes). A gas bed by adding a cooling gas monomer) (e.g., a volatile gas monomer, a liquid). As a rule, the polymer is cooled (e.g., recycled and / or volatile liquid hydrocarbon gas, or which condenses to form in the gas phase and isolated from this phase to form a solid in the polymerization zone which is free or substantially free of liquid. that if any liquid can enter the polymerization zone of the gas-phase polymerization process, the amount of liquid in the polymerization zone is relatively small compared to the amount of polymer present. This is different from the "in solution" process when the resulting polymer is dissolved in solvent, and the difference from the process carried out "in suspension" when the polymer is formed as a suspension in a liquid diluent.

The gas phase process can be carried out in a batch semicontinuous or so-called batch process. "Continuous mode. A preferred operation under these conditions is when the monomer is continuously recycled to the stirred polymerization zone containing the polymerization catalyst, the freshly produced monomer replaces the co-polymerized monomer and the monomer produced is continuously or intermittently discharged from the polymerization zone at a rate comparable to polymerization rate. zone, together with the resulting polymer, is replaced by fresh catalyst added to the polymerization zone.

Methods for the preparation of polyethylene, ethylene and polypropylene copolymers by gas-phase polymerization in a fluidized bed reactor are known in the art. This process can be carried out, for example, in a vertical cylindrical reactor equipped with a perforated distribution plate which serves both as a support for the bed and at the same time as a means for distributing the introduced fluidizing gas stream into the bed. The fluidizing gas that circulates in the bed has. to dissipate the polymerization heat from the bed and to feed the monomer needed for the polymerization. Thus, the fluidizing gas typically comprises monomer (s), commonly together with an inert gas (e.g., nitrogen or inert hydrocarbons such as methane, ethane, propane, butane, pentane, or hexane), and optionally hydrogen, which acts as a molecular modifier. weight. The hot fluidizing gas discharged from the top of the bed is optionally passed through a velocity limiting zone (which may be a cylindrical portion of a reactor having a larger diameter) and, if desired, through a cyclone or filters where the fine solids are separated from the gas stream. The hot gas is then passed to a heat exchanger where it is freed from at least a portion of the polymerization heat. The catalysts are preferably introduced into the bed continuously or at regular intervals. At the beginning of the process, the bed comprises a fluidizable polymer which is preferably similar to the target polymer. The polymer is continuously formed in the bed by polymerizing the monomer (s). In a preferred embodiment, the desired fluidized bed height is maintained by continuously discharging the polymer from the bed or discharging the polymer at regular intervals. This process is generally carried out at a relatively low pressure, for example 1.0, and at temperatures, for example, 50 ° C until the bed is kept below a sintering temperature of the fluidized polymer, thereby avoiding settling problems.

MPa to 5.0 MPa, 135 ° C. temperature

In the gas phase polymerization of olefins in a fluidized bed reactor with heat, as a result of the exothermic polymer reaction, it is generally discharged from the polymerization zone by means of a fluidizing gas stream as described above. The hot gas leaving the top of the bed is passed through one or more heat exchangers where it is cooled. The cooled reaction gas, together with any freshly produced gas, is subsequently introduced into the bottom of the bed. In the gas-phase polymerization process of a fluidized bed reactor according to the invention, it is desirable to cool said bed (and thereby increase operation efficiency) by introducing a volatile fluid into the bed under conditions where the bed liquid evaporates and thereby absorbs additional polymerization heat from the bed. as a result of the effect of "concealed heat evaporation. After the hot recycle gas from the bed enters the heat exchanger, the volatile liquid may condense. In one embodiment of the invention, the volatile liquid is separated from the recycle gas and introduced into the bed separately. For example, the volatile liquid may be separated and injected into the bed. In another embodiment of the invention, the volatile liquid is introduced into the bed together with the recycle gas. Thus, the volatile liquid may condense from the fluidizing gas stream leaving the reactor and may be fed back into the bed together with the recycle gas or may be isolated from the recycle gas and then introduced into the bed.

A method of condensing a liquid in a recycle gas stream and re-introducing a mixture of gas and entrapped liquid into the bed is described in European patent applications EP-A 0089691 and EP-A 0241947. It is preferred that the condensed liquid is introduced into the bed separately after isolation from the recycle gas as described in U.S. Patent 5,541,270.

When the catalysts of the invention are used in an integrated process designed to prepare higher pyrolymers, i. if component (d) is present, a variety of process type choices are offered. These options include "in series" processes where trimerization, subsequent polymerization is performed in separate but interconnected reactors, and "in situ methods" where both steps are performed in the same reactor.

In the in situ gas phase polymerization process, for example, component (d) in liquid may be introduced into the polymerization reaction zone in a form, for example in the form of a solution, in a substantially inert liquid diluent. Components (a), (b), (c of any and (d) may be independently added to a portion of the meter reactor simultaneously, sequentially or in isolation, and under these conditions it is preferred that the liquid containing the component (s) is injected into the meter zone. The diameter of the droplets preferably ranges from 1 µm to 1000 µm.

No. 0593083 discloses a gas phase catalyst. The processes described in EP-A-0593083 can, if desired, be suitably used in carrying out the polymerization process of the invention.

European Patent Application Process for EP Polymerization

Although not normally required, the catalyst may be contacted with water, alcohols, acetone, or other suitable catalysts after completion of the polymerization or copolymerization or, if necessary, to terminate the copolymerization or polymerization or at least temporarily deactivate the catalyst or catalyst component of the invention. catalyst deactivators in a manner known to those skilled in the art.

The trimerization catalyst is preferably (but optionally) in front of the polymerization catalyst, thereby introducing the parent monomer prior to introduction.

However, it adds the desired comonomer ratio (s) of the polymerization catalyst to the desired comonomer composition by initially introducing a fresh comonomer or by initiating a trimerization reaction before or during the polymerization catalyst.

by introducing deployment

In the presence of component (d), the process of the invention provides polymers and copolymers, in particular ethylene polymers, at high productivity (based on the amount of polymer or copolymer produced per unit weight of complex used in the catalyst system). That is, a relatively small amount of transition metal complexes is consumed in commercial processes using the process of the invention. This also means that when the polymerization process of the invention is carried out under conditions where the polymer is isolated without separation of the catalyst, in other words, if the catalyst or its residues are left in the polymer (such as most commercial slurry or polymerization processes). then the amount of transition metal complex in the polymer produced is very small.

By varying the ratio of components (a), (b), optionally (c) and (d), and / or by adding other comonomers, it is possible that the catalysts of the invention provide a wide range of branched polymers which will differ in density and other important physical properties !.

The range of polyethylene polymers obtainable by this method includes high density polyethylene, medium density polyethylene, low density ultra low density polyethylene, and polymers of a density of 0.91 to 0.93, and particularly important. they are in the field as linear low density polyethylene. These polymers and copolymers are widely used in the production of flexible blown or cast films.

polyethylene, elastomeric materials which are generally labeled

Also contemplated are poly (1-hexane), poly (1-octene) and the like, which are, for example, copolymers of 1-hexene and propylene, 1-hexene and 1-octene, and terpolymers such as ethylene, 1-hexene and vinyl acetate.

Dienes may also be incorporated into the polymer products to allow crosslinking, for example in the case of elastomers and meshes and various cables.

Depending on the possible minimum amount of acid scavenger to the polymer, these will generally be approximately 25 mg / l to 1 mg / l to 1000 mg / l and based on the polymer.

For example, the use of a polymer product is the formulation to generally incorporate additives such as antioxidants, stabilizers and the like. additives are incorporated in amounts

2000 mg / l, more often about 50 more commonly 00 mg / l to 1000 mg / l,

In use, the polymers or copolymers produced by the process of the invention in powder form are conventionally compressed into pallet form. Examples of the use of the polymer compositions made by the invention include fiber forming, extrusion of films and sheets, spunbonding, molding of products or thermal

Polymers forming products etc.

blown or cast into foils or can be used to produce various molded or embossed articles such as tubes and containers such as bottles and barrels. Based on the knowledge of those skilled in the art, a specific additive package can be selected for each application. Examples of additional additives include glidants, antistatic agents, agents, release agents, primary and secondary antioxidants, brighteners, nucleating agents, UV stabilizers, and the like. Classes of additives are known in the art and include phosphite antioxidants, hydroxylamine (e.g., N, N-dialkylhydroxylamine) and amine oxide (e.g., dialkylmethylamine oxide) antioxidants, hindered amion light (UV) stabilizers, phenolic stabilizers, benzofuranone, and the like. Various additives added to stabilizers

olefin polymers They are disclosed in U.S. Pat 4 318,845, US 4 325 863 US 4 590 231, US No. 4,668,721, US 4 876,300, US 5 175 312 US 5 276 076, US No. 5,326,802, US 5 344,860, US 5,596,033 and US 5 625 090th Polymeric

fillers such as silica, glass fibers, talc and the like, nucleating agents and coloring agents can also be added to the compositions.

The following examples are illustrative only and are not to be construed as limiting the scope of the invention as set forth in the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

All operations were performed under anaerobic conditions. Solvents and gases were dried and degassed by standard procedures. The chemicals were purchased from Aldrich Chemical Company unless otherwise specified. Methylalumoxane (MAO) and modified methylalumoxane (MMAO) were purchased from Witco in the form of 10% w / w. solutions in toluene, respectively. in heptanes. (2-Methoxyphenyl) ₂ -PN (Me) P (2-methoxyphenyl) ₂ was synthesized according to literature procedures (see Example 12 of WO 97/37765) Cr (p37 tolyl) Cl ₂ (THF) ₃ was synthesized according to the procedure described in the literature (Daly JJ; Seeden. RPAJChemi. Soc. A, 1967, p. 736) The reaction products were analyzed by GCMS using 50 mx 0.3 mm internal diameter columns, CP sil. CBS-MS, df = 0, 4 pm, initial temperature -30 ° C, duration 1 min, heating rate 7 ° C / min, final temperature 280 ° C and duration 5 min Molar amounts of catalyst are based on the molar amount of chromium source in their preparation.

Example 1

A Schlenk tube was charged with CrCl ₃ (THF) ₃ (8 mg, 0.02 mmol) and (2-methoxyphenyl) ₂ PN) MeP (2-methoxyphenyl) ₂ (10 mg, 0.02 mmol), 10 was added. ml THF and the solution was stirred for 2 h. After this time, the solvent was removed under reduced pressure and the resulting solid was suspended in 50 mL of toluene. MAO (4.2 mL, 6.0 mmol, 300 equiv) was added and a green solution was immediately observed. The solution was placed under an ethylene atmosphere (0.1 µm). Immediate exotherm was observed. The reaction was allowed to proceed for 60 min, during which the vessel was left open to allow ethylene feed at 0.1 MPa. The catalyst was then deactivated by the addition of 50 ml of dilute aqueous HCl, the organic layer was separated and dried over MgSO ₄ . The weight of the product obtained from the Schlenk reaction vessel was 10.3 g.

GCMS analysis of the reaction products provided the following product distribution:

butenes wt. total product 0.04

1-hexene 82,17 2-hexene 0.44 3-hexene 0.15 1-octene 1.37 decenes 14.39 C12 olefins 0.20 C14 olefins 0.78 C16 olefins 0.00 C18 olefins 0.00 Example 2 He used the procedure of Example 1, except that: is instead The MAO used 300 equiv. MMAO (4.2 ml, 6, mmol). The weight of the product was 8.8 g. Example 3 He used the procedure of Example 1 except

that 100 equivalents were used instead of MAO. (iBu ₂ AlO) ₂ (2.0 M solution in toluene, 1.0 mL, 2.0 mmol). The weight was 1.3 g.

Example 4

The procedure of Example 1 was followed except that CrCl ₂ (3 mg, 0.02 mmol) was used instead of CrCl ₃ (THF) ₃ . The weight of the product was 5.6 g.

Example 5

Schlenk flask (9 mg, 0.02 mmol) with methoxyphenyl) ₂ (10 mg, charged with Cr (p-tolyl) Cl ₂ (THF) ₃ and (2-methoxyphenyl) ₂ PN (Me) P (20.02 mmol) , 50 mL of toluene was added and the solution was stirred for 5 min, MMAO (4.2 mL, 6.0 mmol, 300 equiv) was added, the solution was placed under an ethylene atmosphere (1 MPa) and the reaction was allowed to proceed for 60 min. The reaction mixture was further worked up as described in Example 1. The weight of the product was 11.0 g.

Example 6

The procedure of Example 1 was repeated except that 0.04 mmol (20 mg) of (2-methoxyphenyl) ₂ PN (Me) P 2 -methoxyphenyl) 2 was used before 0.02 mmol. The weight of the product was 9.5 g.

Example 7

The procedure of Example 2 was repeated except that 0.01 mmol (5 mg) of (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ was used before 0.02 mmol. The product weight was 3.3 g.

Example 8

A Schlenk tube was charged with (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ (415 mg, 0.8 mmol) and CrCl ₃ (THF) ₃ (300 mg, 0.8 mmol) and 30 mL was added. ml of dichloromethane. Almost immediately a clear blue solution was formed, which was then stirred for 2 h. After this time, the solvent was removed under reduced pressure to give a blue solid; it was rinsed with diethyl ether and dried under vacuum. An additional Schlenk tube was charged with mg of this compound and 50 mL of toluene was added. MMAO (16.8 mL, 24 mmol, 300 equiv) was added and the solution was placed under an ethylene atmosphere (1 MPa). The reaction was allowed to proceed for 60 min, during which the vessel was left open to allow ethylene (10 bar). The reaction mixture was as described in Example 1. The weight of the product was

2.5 g.

be completed further processed

Example 9

Preparation of MAO on silica

In an inert atmosphere, silica was added to the vessel (prepared according to the procedures described in Example 37.1 of International Application WO 99/12981; silica was supplied by Crosfield as batch ES70X, annealed overnight at 280 ° C, 20.5 g after annealing) toluene ( 200 ml). The suspension was mechanically stirred and MAO (1.5 M, 62.1 mmol, 41.4 mL) was added via syringe. The mixture was stirred at 80 ° C for 1 h, then excess toluene was removed and the mixture dried under vacuum to give 15% w / w. MAO on silica in quantitative yield.

Trimerization using supported catalyst

A Schlenk flask was charged with CrCl ₃ (THF) ₃ (8 mg, 0.02 mmol), 10 mL THF was added and the solution stirred for 2 h. After this time, the solvent was removed under reduced pressure and the resulting solid was suspended in 20 mL of toluene. MAO (1.4 mL, 2 mmol, 100 equiv) was added and a green solution was immediately observed. This solution was then transferred via cannula into a Schlenk tube containing a 15% w / w suspension. MAO on silica (prepared as described above) in toluene (1 g MAO / silica in 30 ml toluene). The green-colored solution was quickly transferred to silica / MAO and the colorless suspension supernatant was stirred and left in the vessel. This was placed under an ethylene atmosphere (0.1 MPa). The reaction was allowed to proceed for 60 min, during which the vessel was left open to allow the addition of ethylene (10 bar). The reaction mixture was further worked up as described in Example 1. The weight of the product was 8.9 g.

% wt. total product

1-hexene 62 octenes 0.28 decenes 30.3

Example 10

A Schlenk flask was charged with CrCl ₃ (THF) ₃ (8 mg, 0.02 mmol) and (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ (10 mg, 0.02 mmol), 10 was added. ml THF and the solution was stirred for 2 h. After this time, the solvent was removed under reduced pressure, the resulting solid was suspended in 10 mL of toluene and MAO (4.2 mL, 6.0 mmol, 300 equiv) was added. This solution was then injected into the autoclave at an ethylene pressure of 0.8 MPa and 50 ° C. The diluent was isobutane. The reaction was allowed to proceed for 1 hour at an ethylene pressure of 20 bar and 50 ° C, and then ethylene gas and isobutane were vented. The reaction products were subsequently treated as described in Example 1. The weight of the isolated product was 40.0 g and the productivity over 1 h was 2000 g / mmol.h. GCMS analysis provided the following product distribution:

% wt. total product butenes

1- hexene

2-hexene

3-hexene octene decene

C12 olefins C14 olefins C16 olefins C18 olefins

0.00

88,37

0, 12 0.00 3.95 6.61 0, 33 0.20 0.00 0.00

Example 11

The method of Example 10 was repeated with the following exceptions; instead of isobutene, 50 ml of toluene and 0.01 mmol of catalyst were used as the diluent. The reaction conditions were maintained at 50 ° C and the ethylene pressure at 0.8 MPa for 60 min. A stable gas absorption profile was observed during the reaction. The weight of the isolated product was 72.7 g and the productivity for one hour was 7270 g / mmol.h (134,700 g / g Cr.h)

ABOUT.

wt. Total product

1-hexene octene decene

1.8

8.7

Example 12

The procedure of Example 11 was repeated except that the following reaction conditions were maintained: temperature 80 ° C, ethylene pressure 20 bar, reaction time 60 min. 0.0025 mmol of catalyst was used. The weight of the isolated product was 141 g and the productivity over

one hour was 56,400 g / mmol.h (1,033,200 g / g Cr.h) % wt. total product 1-hexene 88.8 octenes 1.8 decenes 7.4

Example 13

The procedure of Example 11 was repeated except that the following reaction conditions were maintained: temperature 108 ° C, ethylene pressure 0.8 MPa and reaction time 60 min. 0.01 mmol of catalyst was used. The weight of the isolated product was 51.6 g and the productivity over one hour was 5160 g / mmol.h (95,900 g / g Cr.h) wt%. of total product 1-hexene 86,6 decene 11

Example 14

The procedure of Example 11 was repeated except that hydrogen was introduced into the reactor at a pressure of 1 bar before starting the reaction. 0.01 mmol of catalyst was used. The weight of the isolated product was 94.7 g and the productivity over one hour was 9470 g / mmol.h (175,300 g / g Cr.h) wt%. total product

1-hexene 82 octenes 0.45 decenes 13.2

Example 15

The procedure of Example 11 was repeated except that 0.01 mmol of supported catalyst prepared as described in Example 8 was used. % (g.h.h) wt. total product

1-hexene 89 octenes 0.58 decenes 7.9 Example 16

The procedure of Example 11 was repeated except that 100 mL of 1-butene was added to the reactor prior to the start of the reaction and 400 mL of toluene diluent was used. The following reaction conditions were maintained: temperature of 80 ° C and ethylene pressure of 0.4 MPa. 0.02 mmol of catalyst were used. The weight of the isolated product was 49.4 g and the productivity over one hour was 2470 g / mmol.h (46,125 g / g Cr.h) wt%. total product 60

1-hexene octene decene

10.9

Example 17

The procedure of Example 1 was repeated except that the reaction in this case lasted 90 minutes and the weight of the product was recorded by weighing the weight of the product.

taken from reaction moments during Schlenk containers reactions. at different times Time (min) 15 30 45 60 90 obtained weight (g) 2,7 5,2 7.6 10,0 13,0 GCMS analysis Product after 90 min.poskytla

the following product distribution:

% wt. total product

butenes 0.00 1-hexene 64.10 2-hexene 0.13 3-hexene 0.00 octenes 0.44 decenes 28,93 C12 olefins 0, 13 C14 olefins 4, 99 C16 olefins 0.00 C18 olefins '0.59

Example 18

The procedure of Example 2 was repeated except that 20 ml of toluene and 20 ml of 1-dodecene were used at the start of the reaction.

The weight of the product was 2.1 g.

% wt. total product

1-hexene 37 decene 27 C16 olefins 39

Example 19 ₍

The procedure of Example 2 was repeated except that 20 ml of toluene and 20 ml of 1-tetradecene were used at the start of the reaction. The weight of the product was 3.2 h.

% wt. total product

1-hexene 35, 3 decene 6.7 C18 olefins 50.8

Example 20

The procedure of Example 8 was repeated except that 20 ml of toluene was used and 20 ml of 1-dodecene was added at the beginning of the reaction, in which case the reaction lasted 4.5 hours. The weight of the product was 7.5 g.

% wt. total product

1-hexene 38 decene 24 C16 olefins 38

Example A (control)

The procedure of Example 1 was repeated except that 1,2-bis (diphenylphosphino) ethane (8 mg, 0.02 mmol) was used in place of (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ . No product was formed.

Example 21

The procedure of Example 1 was followed except that tris (2-methoxymethoxyphenyl) phosphane (18 mg, 0.05 mmol) was used in place of (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ . The weight of the product was 1.2 g. GCMS analysis of the reaction products provided the following product distribution:

% wt. total product

1-hexene 90.66 2-hexane 2.94 1-octene 2.85 decenes 3.54

Example B (control)

The procedure of Example 20 was repeated except that tri-phenylphosphane (11 mg, 0.04 mmol) was used in place of tris (2-methoxymethoxyphenyl) phosphane. No product was formed.

Example 22 (Co) polymerization of ethylene

The autoclave was charged with isobutane (500 mL) and triethylaluminum (2.0 M solution in toluene, 1.5 mL, 3 mmol). The autoclave was pressurized to 0.8 Mpa ethylene pressure and heated to 50 ° C.

The catalyst (0.02 mmol), prepared as described in Example 8, was then injected as a slurry in 10 mL of toluene. Almost immediately thereafter a Ziegler catalyst slurry (0.05

g), prepared as described in Example A of U.S. Pat. No. 5,470,812, as a toluene suspension. The reaction was allowed to proceed for 1 h at 50 psi ethylene pressure. After this time, ethylene and isobutane gas were vented. The resulting polymer was washed with dilute aqueous HCl, followed by methanol, and dried in vacuo. The weight of the isolated polymer reached 36.0 g. NMR spectroscopy of the polymer showed the presence of butyl branches, indicating that the product was a copolymer of ethylene and 1-hexene.

Example 23 (Ko) Polyineration of Ethylene

The supported catalyst (0.01 mmol) was prepared as described in Example 9 in 40 ml of toluene. In a separate Schlenk tube, [rac (ethylene-bridged bisindenyl) -propionium dichloride] (mg, 0.01 mmol) was dissolved in 10 mL of toluene and MMAO (7 mL, 10.0 mmol, 1000 equiv) was added. This second solution was added via cannula to the supported catalyst slurry and the resulting slurry was stirred under an ethylene atmosphere at 1 bar. The reaction was allowed to proceed for 60 min, during which the vessel was left open to allow the addition of ethylene (10 bar). The catalysts were then deactivated by the careful addition of 50 ml of dilute aqueous HCl. Both the organic and aqueous fractions were subsequently added to 500 ml of acetone, causing precipitation of the prepared polymer. The polymer was rinsed with additional portions of acetone and dried under vacuum. The weight of the isolated polymer was 3.4 g. NMR Spectroscopy of the polymer showed the presence of butyl branches, indicating that the product was a copolymer of ethylene and 1-hexene.

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PATENT CLAIMS

Claims (45)

A catalyst comprising (a) a source of chromium, molybdenum or tungsten; (b) a ligand comprising at least one of a phosphorus, arsenic or antimony atom attached to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, except that all of these polar substituents are a phosphane, arsenic or stibane group; and optionally c) activator. (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) ₂ , (2-ethoxyphenyl) ₂ PN (Me) P (2-ethoxyphenyl) ₂ (2-isopropoxyphenyl) ₂ PN (Me) P (2-isopropoxyphenyl) ) ₂ (2-hydroxyphenyl) ₂ PN (Me) P (2-hydroxyphenyl) ₂ (2-nitrophenyl) ₂ PN (Me) P (2-nitrophenyl) ₂ (2,3-dimethoxyphenyl) ₂ PN (Me) P ( 2,3-dimethoxyphenyl) ₂ (2,4-dimethoxyphenyl) ₂ PN (Me) P (2,4-dimethoxyphenyl) ₂ (2,6-dimethoxyphenyl) ₂ PN (Me) P (2,6-dimethoxyphenyl) ₂ ( 2,4,6-trimethoxyphenyl) ₂ PN (Me) P (2,4,6-trimethoxyphenyl) ₂ (2-dimethoxyphenyl) (2-methylphenyl) PN (Me) P (2-methylphenyl) ₂ , [2- (dimethylamino)] phenyl] ₂ PN (Me) P [2- (dimethylamino) phenyl] ₂ (2-methoxymethoxyphenyl) ₂ PN (Me) P (2-methoxymethoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (ethyl) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (phenyl) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PN (Me) N (Me) P (2-methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PCH ₂ P (2 -methoxyphenyl) ₂ (2-methoxyphenyl) ₂ PCH ₂ CH ₂ P (2-methoxyphenyl) ₂ tri (2-methoxymethoxyphenyl) phosphane, ie tri (2-methoxyphenyl) phosphane. (2-methoxyphenyl) (phenyl) PN (Me) P (phenyl) ₂ , (2-methoxyphenyl) ₂ PN (Me) P (phenyl) ₂ , (2-methoxyphenyl) (phenyl) PN (Me) P (2- methoxyphenyl) (phenyl), silver, sodium hexafluoroantimonate, boroxines, NaBH ₄ , trimethylboron, triethylboron, dimethylphenylammoniumtetra (phenyl) borate, trityltetra (phenyl) borate, triphenylboron, dimethylphenylammoniumtetra (pentafluorophenyl) boronate (pentafluorophenyl) borane sodium fluoride) phenyl sodium borate, H ⁺ (Oet ₂ ) 2 [(bis-3,5-trifluoromethyl) phenyl] borate, trityltetra (pentafluorophenyl) borate and tris (pentafluorophenyl) boron or mixtures thereof. Catalyst according to claim 1, supported on a support. 3. A supported catalyst having a productivity per mole of catalyst of at least 50%, preferably at least 70% of its productivity, unless supported on a support which preferably comprises (a) source of transition metal III. to X groups; (b) a ligand containing at least one of a phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but except where:. all of these polar substituents are a phosphane, arsenic or stiban group; and optionally c) activator. 4. The catalyst of claim 3 having olefin trimerization. productivity Catalyst according to claim 3 or 4, wherein the support is selected from silica, alumina, MGCl ₂ , zirconium dioxide, polyethylene, polypropylene, polystyrene or poly (aminostyrene). Catalyst according to claim 3, 4 or 5, wherein component a) is a source of chromium, molybdenum or tungsten. Catalyst according to any one of the preceding claims, wherein component a) is a chromium source. Catalyst according to any one of the preceding claims, wherein the ligand component b) has the general formula (R ¹ ) (R ² ) XYX (R ³ )) (R ⁴ ) or (R ¹ ) (R ² ) (R ³ ), wherein X represents a phosphorus, arsenic or antimony atom; Y is a linking group; and R ¹ R ² R ³ R ⁴ are each independently a hydrocarbyl group, a heterohydrocarbyl group or a substituted heterohydrocarbyl group, at least one of which in both formulas has a polar substituent which is not a phosphane, arsenic or stibane group and any of the R groups ¹ to R ⁴ independently of one another may be linked to one or more of the groups or a bridging group Y to form a cyclic structure together with X or X and Y. The catalyst of any preceding claim, wherein X is a phosphorus atom. Catalyst according to claim 8 or 9, wherein the optionally substituted hydrocarbyl or heterohydrocarbyl groups R ¹ , R ² , R ³ , R ^{4 are} independently selected from methyl, ethyl, ethylenyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy (ie OC _S H ₅ ), tolyloxy (ie -OC ₆ H ₄ , CH ₃ , xylyloxy, mesityloxy, dimethylamino, diethylamino, methylethylamino, thiomethyl, thiophenyl, trimethylsilyl or dimethylhydrazyl. Catalyst according to any one of the preceding claims 8 to 10, wherein R ¹ to R ⁴ having polar substituents are each independently selected from substituted phenyl, substituted naphthyl or substituted anthracenyl. The catalyst of claim 11, wherein the polar substituents are independently selected from methoxy, ethoxy, isopropoxy, C 3 -C 3 alkoxy, phenoxy, trimethylsiloxy, methylsulfanyl methoxymethyl, groups, groups, groups, nitro, and stibane groups. The catalyst of claim 12, wherein R ¹ to R ⁴ having polar substituents are each independently o 53 methoxyphenyl or o-methoxymethoxyphenyl. The catalyst according to any one of the preceding claims 8 to 13, wherein all of R ¹ to R ⁴ have an independent polar substituent which is not a phosphane, arsenic or stibane group. Catalyst according to any one of the preceding claims 8 to 14, wherein Y represents a hydrocarbyl bridging group, a substituted hydrocarbyl bridging group, a heterohydrocarbyl bridging group, a substituted hydrocarbyl bridging group or a substituted heterohydrocarbyl bridging group or a substituted heterohydrocarbyl bridging group. The catalyst of claim 15, wherein Y is methylene, 1,2-ethane, 1,2-phenylene, 1,3-propane, 1,2-catechol, 1,2-dimethylhydrazine or -N (R ⁵ ) -, wherein R ⁵ represents a hydrogen atom, a hydrocarbyl group or a substituted hydrocarbyl group. The catalyst of claim 16, wherein Y is -N (R ⁵ ) -, wherein R ⁵ is hydrogen, C 1 -C 6 alkyl, or phenyl. A catalyst according to any preceding claim wherein component (b) is selected from the following compounds: Catalyst according to any of the preceding claims, wherein component (c) is selected from trimethylaluminium (TMA), triethylaluminium (TEA), triisobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminum dichloride, dimethylaluminum dichloride, alumoxanes, tetrafluoroboric acid etherate, tetrafluoroborate A catalyst for trimerizing and polymerizing 1-olefins, further comprising one or more catalysts (d) suitable for the polymerization, oligomerization or other chemical transformation of olefins. 20 atoms of pentafluorophenoxy, dimethylamino, tosyl, methylthiomethyl, 1,3-oxazolyl methoxymethoxy, hydroxyl amino, sulfate, phosphane, arsenic. The catalyst of claim 20, wherein the catalyst (d) is selected from Ziegler-Natta catalysts, metallocene catalysts, monocyclopentadienyl catalysts or limited geometry catalysts, thermally activated supported chromium oxide catalysts, late transition metal catalysts and one-site polymerization catalysts. catalysts. Catalyst according to any one of the preceding claims, having a trimerization productivity of at least 15,000 g of product per mmol of catalyst per hour, preferably of at least 30,000 g of product per mmol of catalyst per hour, at a temperature of 110 ° C or less and partial pressure. ethylene of 2.1 MPa or less. An olefin trimerization catalyst wherein catalyst productivity decreases at a rate of less than 10% per hour. Catalyst for the trimerization of ethylene having a trimerization productivity of at least 15,000 g of product per mmol of catalyst per hour, preferably at least 30,000 g of product per mmol of catalyst per hour, at a temperature of 110 ° C or less and ethylene partial pressure 2 1 MPa or less. Catalyst according to any one of the preceding claims 22 to 24, supported on a support, preferably on a support selected from silica, alumina, MgCl ₂ , zirconia, polyethylene, polypropylene, polystyrene or poly (aminostyrene). 26. A process for trimerizing olefins comprising contacting a monomeric olefin or olefin mixture under trimerization conditions with a catalyst comprising: (a) source of transition metal III. to X. groups; (b) a ligand comprising at least one of a phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, except that all of these polar substituents are a phosphane, arsenic or stibane group; and optionally c) activator. The method of claim 26, wherein the catalyst is as defined in any one of claims 1 to 25. 28. The method of claim 26 or 27, wherein the olefin or olefin mixture is further contacted by polymerization, transformations incorporating the product. 29. The process of ethylene. with another catalyst d) suitable for oligomerization or other chemical olefins, such that trimerization products into a higher polymer or other chemical according to any one of claims 26 to 28, characterized in that the monomeric olefin is A process according to any one of claims 26 to 28, wherein the olefin mixture comprises ethylene and one or more monoolefins having from 3 to 36 carbon atoms. 31. The method of claim 30, wherein the monoolefin of claim 30 is a C 3 -C 36 monoolefin. The effect of carbon is A process according to claim 31, wherein the C 4 -C 20 monoolefin comprises butene, hexene, decene, C 12 olefin or C 14 olefin. A process according to any one of claims 26 to 32, wherein at least 85 wt. preferably at least 90 wt. The product of the trimerization reaction is one of the following products: 1-hexene, 1-octene, 1-decene, C12 olefin, C14 olefin, C16 olefin or C18 olefin. Process according to any one of claims 26 to 33, characterized in that the reaction temperature is less than 100 ° C and / or the reaction pressure is less than 3.0 MPa. 35. The method of any one of claims 26 to 34, wherein the time spent in the polymerization reactor is less than 4 hours, preferably less than 3 hours. 36. A process according to any one of claims 26 to 35, wherein the reaction is carried out in solution, in suspension or in the gas phase. 37. The process of claim 36, wherein the reaction is carried out in the gas phase in a fluidized bed. 38. The process of claim 28 wherein the trimerization reactor is located upstream or downstream of the at least one polymerization or oligomerization reactor. The method of claim 28, wherein the trimerization reactor is incorporated into the reaction loop of at least one polymerization or oligomerization reactor. 40. The method of claim 39, wherein the trimerization reactor is incorporated into a side stream discharged from the reaction loop. 41. The process of claim 28 wherein the trimerization reaction product is produced in or introduced into at least one polymerization or oligomerization reactor. Process according to any one of the preceding claims 28 and 38 to 40, characterized in that at least one trimerization reaction product is separated from the remainder of the trimerization reaction product before optionally re-introduction into the polymerization or oligomerization reactor. Process according to any one of claims 26 to 42, characterized in that the trimerization reaction is carried out in the presence of a hydrogen source and / or a halide. Use of a mixture of components (a), (b), optionally (c) and optionally (d) as defined in any one of claims 1 to 25, as a catalyst for the trimerization of olefins. Use of a mixture of components (a), (b), (d) and optionally (c) as defined in any one of claims 1 to 25 as a catalyst for the homopolymerization of ethylene producing polyethylene having a density of 960 g / cm ³ or less, preferably 940 g / cm ³ or less, and more preferably 920 g / cm ³ or less.